三(3-甲酰基苯基)铋 | 146800-14-8

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 中文名称: 三(3-甲酰基苯基)铋
• 英文名称: tris(3-formylphenyl)bismuthine
• 英文别名: tri(4-formylphenyl)bismuthine
• CAS: 146800-14-8
• 化学式: C₂₁H₁₅BiO₃
• 分子量: 524.329
• InChiKey: FCAWITOCCGKOJM-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.64
• 重原子数：
  25
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.0
• 拓扑面积：
  51.2
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  对溴甲苯 、 三(3-甲酰基苯基)铋 在 [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene](3-chloropyridyl)palladium(ll) dichloride 、 三苯基膦 、 cesium fluoride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 8.0h， 以15%的产率得到4-(4-甲基苯基)苯甲醛
  参考文献：
  名称：

  Mechanism insight and scope of PEPPSI-catalyzed cross-coupling reaction between triarylbismuth and arylbromide

  摘要：

  In this paper we report the first cross-coupling reaction of Ar3Bi with Ar'X mediated by Pd-NHC complexes by keeping the ability of Ar3Bi to transfer the three aryl moieties. Investigations were carried out in order to minimize the quantity of the side product Ar-Ar coming from the conversion of Ar3Bi. The results showed that PEPPSI IPr was a good catalyst precursor. Efforts were focussed on the rule of each additive such as PPh3 and the base. It was notably found that the presence of PPh3 (ratio PEPPSI IPriPPh(3): 1/1) was essential to keep the process efficient. Therefore NHC-Pd-PPh3 has been assumed as being the catalytic species. Under the optimized reaction conditions the concomitant formation of the undesired biaryl side product was restricted to its inherent formation consecutive to the reduction of the catalyst precursor to Pd(0). In a last study, the scope and the limitation of the new catalytic methodology were examined and a large range of unsymmetrical biaryl compounds Ar-Ar' bearing various substituents from strongly electron-donating to electron-withdrawing ones have been prepared and fully characterized. (C) 2016 Elsevier B.V. All rights reserved.

  DOI：

  10.1016/j.molcata.2016.07.016
• 作为产物：
  描述：

  3-(benzaldehyde diethyl acetal)magnesium bromide 在 盐酸 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.5h， 生成 三(3-甲酰基苯基)铋
  参考文献：
  名称：

  铜介导的三价Arylbismuth试剂通过苯酚的O-芳基化反应合成高度官能化的二芳基醚

  摘要：

  高度官能化二芳基醚是由铜制备（II），乙酸介导的O-芳基化使用三价organobismuthanes酚的反应。该反应简单的条件下进行，并容许的官能团的广泛的多样性的苯酚和对有机铋试剂。通过在氧气气氛下进行反应，可以使用亚化学计量的催化剂。也报道了吡啶酮的N-芳基化。

  DOI：

  10.1002/chem.201303684

文献信息

• Atom-economic threefold cross-couplings of triarylbismuth reagents with 2-halobenzaldehydes and pot-economic in situ Wittig functionalizations with phosphonium salts
  作者：Maddali L. N. Rao、Ritesh J. Dhanorkar

  DOI：10.1039/c4ra13348j

  日期：——

  In this paper we report an efficient pot-economic methodology for the synthesis of ortho-olefinated biaryls. This has been achieved through an atom-economic threefold cross-coupling of triarylbismuth reagents with 2-halobenzaldehydes followed by pot-economic in situ Wittig olefination. The overall process is a pot-economic straightforward synthesis of ortho-olefinated biaryls from 2-halobenzaldehydes, triarylbismuth reagents and phosphonium salts. This pot-economic approach was applied to the formal synthesis of medicinally important Eupomatilone-6.

  本文报道了一种高效的原位Wittig烯化反应方法，用于合成邻烯基联苯。通过三芳基铋试剂与2-卤代苯甲醛的三重交叉偶联，继而进行原位Wittig烯化，实现了这一目标。整个过程是从2-卤代苯甲醛、三芳基铋试剂和膦盐出发，高效简便地合成邻烯基联苯。这一方法已成功应用于重要的药用成分Eupomatilone-6的正式合成中。
• Pd(0)/C-catalyzed cross-couplings of acyl chlorides with triarylbismuths as atom-efficient sub-stoichiometric multi-coupling reagents
  作者：Maddali L.N. Rao、Deepak N. Jadhav、Varadhachari Venkatesh

  DOI：10.1016/j.tetlet.2009.05.003

  日期：2009.7

  Aromatic and hetero-aromatic acyl chlorides were efficiently cross-coupled with triarylbismuths as atom-efficient nucleophilic organometallic coupling reagents in sub-stoichiometric amounts using catalytic Pd(0)/C. Thus, the coupling reactions of various triarylbismuths with a variety of acyl chlorides furnished a plethora of both symmetrical/unsymmetrical aromatic and hetero-aromatic ketones in high

  使用催化的Pd（0）/ C，亚化学计量的芳香族和杂芳香族酰氯与三芳基铋有效地交叉偶联，成为原子有效的亲核有机金属偶联剂。因此，各种三芳基铋与各种酰氯的偶联反应以高收率提供了大量对称/不对称的芳族和杂芳族酮。
• Atom-Efficient Vinylic Arylations with Triarylbismuths as Substoichiometric Multicoupling Reagents under Palladium Catalysis
  作者：Maddali L. N. Rao、Deepak N. Jadhav、Varadhachari Venkatesh

  DOI：10.1002/ejoc.200900487

  日期：2009.9

  The first atom-efficient arylation of vinylic iodides was achieved by using triarylbismuths as substoichiometric multicoupling reagents under palladium catalysis. Vinylic iodides were efficiently coupled with electronically divergent triarylbismuths to furnish the corresponding arylated products in short reaction times. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

  通过在钯催化下使用三芳基铋作为亚化学计量的多偶联试剂，实现了乙烯基碘的第一个原子有效芳基化。乙烯基碘化物与电子发散的三芳基铋有效偶联，以在较短的反应时间内提供相应的芳基化产物。(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)
• Copper‐Promoted N‐Arylation of the Imidazole Side Chain of Protected Histidine by Using Triarylbismuth Reagents
  作者：Hwai‐Chien Chan、Bianca Bueno、Adrien Le Roch、Alexandre Gagnon

  DOI：10.1002/chem.202102186

  日期：2021.9.20

  The N-arylation of the side chain of histidine by using triarylbismuthines is reported. The reaction is promoted by copper(II) acetate in dichloromethane at 40 °C under oxygen in the presence of diisopropylethylamine and 1,10-phenanthroline and allows the transfer of aryl groups with substituents at any position of the aromatic ring. The reaction shows excellent functional group tolerance and is applicable

  报道了使用三芳基铋对组氨酸侧链进行 N-芳基化。在二异丙基乙胺和 1,10-菲咯啉的存在下，在 40 °C 的二氯甲烷中，乙酸铜 (II) 促进了该反应，并允许在芳环的任何位置具有取代基的芳基转移。该反应显示出优异的官能团耐受性，适用于组氨酸位于 N 端的二肽。在组氨酸占据 C 末端的二肽中观察到组氨酸引导的主链 NH 芳基化。
• Mechanism insight and scope of PEPPSI-catalyzed cross-coupling reaction between triarylbismuth and arylbromide
  作者：Bénédicte Cassirame、Sylvie Condon、Christophe Pichon

  DOI：10.1016/j.molcata.2016.07.016

  日期：2016.12

  In this paper we report the first cross-coupling reaction of Ar3Bi with Ar'X mediated by Pd-NHC complexes by keeping the ability of Ar3Bi to transfer the three aryl moieties. Investigations were carried out in order to minimize the quantity of the side product Ar-Ar coming from the conversion of Ar3Bi. The results showed that PEPPSI IPr was a good catalyst precursor. Efforts were focussed on the rule of each additive such as PPh3 and the base. It was notably found that the presence of PPh3 (ratio PEPPSI IPriPPh(3): 1/1) was essential to keep the process efficient. Therefore NHC-Pd-PPh3 has been assumed as being the catalytic species. Under the optimized reaction conditions the concomitant formation of the undesired biaryl side product was restricted to its inherent formation consecutive to the reduction of the catalyst precursor to Pd(0). In a last study, the scope and the limitation of the new catalytic methodology were examined and a large range of unsymmetrical biaryl compounds Ar-Ar' bearing various substituents from strongly electron-donating to electron-withdrawing ones have been prepared and fully characterized. (C) 2016 Elsevier B.V. All rights reserved.